JP2004346239A - Wax-metallic soap composite emulsion dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an emulsion dispersion exhibiting by far excellent surface modifying ability of a substrate compared with a conventional wax emulsion dispersion or a fatty acid metal salt emulsion dispersion. <P>SOLUTION: The wax-metallic soap composite emulsion dispersion contains composite particles containing (a) a hardly water-soluble wax and (b) a hardly water-soluble metallic soap. The (a/b) weight ratio is preferably 0.04-4 and the volume-average particle diameter of the composite particle is preferably 0.01-60 μm. The method for the production of the wax-metallic soap composite emulsion dispersion containing the hardly water-soluble wax (a) and the hardly water-soluble metallic soap (b) comprises a step to mix an emulsion dispersion containing the particle (a) and an aqueous emulsion dispersion containing the particle (b). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００８２】
＜比較例１〜６＞
（ａ１）、（ａ２）又は（ａ３）の乳化分散体及び（ｂ１）、（ｂ２）又は（ｂ３）の乳化分散体をそれぞれ順に比較用の乳化分散体１１〜１６とした。
【００８３】
本発明の乳化分散体１〜９（実施例１〜９）及び比較用の乳化分散体１〜６（比較例１〜６）について、体積平均粒子径、基材表面改質能（表面摩擦調整能及び耐水化能）を評価し結果を表２に示した。
【００８４】
＜比較例７〜１５＞
表２に記載したように比較用の乳化分散体１〜６を組み合わせて、基材表面改質能の評価直前にスチレン−ブタジエンラテックスに投入・混合した後、基材表面改質能を評価し、これらの結果を表２に示した。
【００８５】
＜体積平均粒子径の測定方法＞
レーザー光回折散乱式粒度分布測定装置｛商品名：マイクロトラック（ＭＩＣＲＯＴＲＡＣ ＵＰＡ、Ｌｅｅｄｓ ａｎｄ Ｎｏｒｔｈｅｒｕｐ製）、条件（レーザー光波長；７８０ｎｍ、測定温度；２５℃、分散媒；水、計測時間１分）｝により測定した。
【００８６】
＜表面摩擦調整能＞
３００ｍｌガラス製ビーカー（外径７８ｍｍ、高さ１０３ｍｍ）にスチレン−ブタジエンラテックス｛商品名：ＪＳＲ０６９６、ＪＳＲ製｝２００ｇを計り取り、ＤＣスターラー（ポリフッ化エチレン樹脂被覆、丸型細型、外径８ｍｍ、長さ２５ｍｍ）で回転数３００ｒｐｍの攪拌下で、評価サンプル１０ｇ投入し、１０分間攪拌を継続することにより均一に混合した。なお、比較例７〜１５において、表２に記載した重量比率で評価サンプル１０ｇを均一に混合した。すなわち、最初の乳化分散体（表２中、上段）をＤＣスターラーで回転数３００ｒｐｍの攪拌下で投入し、１０分間攪拌を行った後、他方の乳化分散体（表２中、下段）をＤＣスターラーで回転数３００ｒｐｍの攪拌下で投入し、１０分間攪拌を行った。これを上質紙に塗工機｛商品名：マルチラボラトリーコーター１００型、オースギ製｝でバーコーターＮｏ．８を用いて塗工し、１３０℃で１５秒乾燥し、２４時間放置して測定試料を調製した。また、ブランクとして、評価サンプルを投入しない測定試料も調整した。
引き続いて温度２５℃、相対湿度６０％の雰囲気下で表面測定機｛商品名：トライボギア タイプ：１４ＤＲ、ヘイドン製｝を用いて測定試料表面の静摩擦係数を測定した。すなわち、測定試料を切断して２つの試験片（試験片サイズ：治具側：縦１０ｃｍ×横３．５ｃｍ、テーブル側：縦２４ｃｍ×横５ｃｍ）にし、測定治具として３０ｍｍ平面圧子を用い、試験片の塗工面同士を向かい合わせて接した状態で垂直荷重を１ｋｇ、試料引っ張り速度２００ｍｍ／分で１２０ｍｍの距離を滑らせて静摩擦係数（μｓ）を計測した。
【００８７】
＜耐水化能＞
３００ｍｌガラス製ビーカー（外径７８ｍｍ、高さ１０３ｍｍ）にスチレン−ブタジエンラテックス｛商品名：ＪＳＲ０６９６、ＪＳＲ製｝２００ｇを計り取り、２５℃に温度調整しておき、これに、ＤＣスターラー（ポリフッ化エチレン樹脂被覆、丸型細型、外径８ｍｍ、長さ２５ｍｍ）で回転数３００ｒｐｍの攪拌下で、評価サンプル３０ｇ投入し、１０分間攪拌を継続することにより均一に混合した。なお、比較例７〜１５において、表２に記載した重量比率で評価サンプル３０ｇを均一混合した。すなわち、最初の乳化分散体（表２中、上段）をＤＣスターラーで回転数３００ｒｐｍの攪拌下で投入し、１０分間攪拌を行った後、他方の乳化分散体（表２中、下段）をＤＣスターラーで回転数３００ｒｐｍの攪拌下で投入し、１０分間攪拌を行った。得られた混合溶液をクリーンベンチ内で３ＭＩＬ（７６．５μｍ）のフィルムアプリケーターを用いて、ガラス板に塗布し、２４時間２５℃で乾燥させて、測定試料を調製した。また、ブランクとして、評価サンプルを投入しない測定試料も調整した。この測定試料を２５℃の脱イオン水中に浸漬し、測定試料の塗膜が白化するまでの時間を測定した。
【００８８】
【表２】

【００８９】
【発明の効果】
本発明の乳化分散体は、従来のワックス乳化分散体又は脂肪酸金属塩乳化分散体と比較して、極めて優れた基材表面改質能（特に表面摩擦調整能及び耐水化能）を発揮する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a wax-metal soap composite emulsified dispersion.
[0002]
[Prior art]
Amide wax, montan wax or polyolefin wax, cellulose ether dispersant and surfactant (polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl) (E.g., ether, polyoxyethylene alkyl phenyl ether, alkyl sulfate sodium salt, sodium polyoxyethylene alkyl ether sulfate sodium salt) (Patent Document 1), (oxidized) polyethylene wax, polypropylene wax, carnauba wax , Montan wax, microcrystalline wax or caster wax and a surfactant (polyoxyethylene alkyl ether or the like) wax emulsion dispersion (Patent Document 2), polyethylene Wax or polypropylene wax and a monocarboxylic acid glyceride, a wax emulsified dispersion (Patent Document 3), an alkali metal (sodium and potassium) or ammonium salt of a fatty acid, and a surfactant (polyoxyethylene alkyl ether, Fatty acid metal salt emulsified dispersions comprising polyoxyethylene alkylphenyl ether, alkylbenzenesulfonic acid sodium salt and alkyl alcohol sulfate sodium salt (Patent Documents 4 and 5) are known.
[0003]
[Patent Document 1]
JP-A-9-176493
[Patent Document 2]
JP-A-10-287060
[Patent Document 3]
Japanese Patent Publication No. 9-502216
[Patent Document 4]
JP-A-11-256334
[Patent Document 5]
JP-A-1-35745
[0004]
[Problems to be solved by the invention]
However, conventional wax emulsified dispersions or fatty acid metal salt emulsified dispersions may not provide sufficient base material surface modifying ability (surface friction adjusting ability, water resistance, etc.). That is, an object of the present invention is to provide an emulsified dispersion having much better substrate surface modification ability than conventional wax emulsified dispersions or fatty acid metal salt emulsified dispersions.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found that an emulsified dispersion containing specific particles achieves the above object, and have reached the present invention. That is, the feature of the wax-metal soap composite emulsified dispersion of the present invention is that it includes composite particles containing a poorly water-soluble wax (a) and a poorly water-soluble metal soap (b).
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The poorly water-soluble wax (a) includes conventionally known waxes and the like, and can be appropriately selected depending on the purpose of use and application.
In the present invention, the term “poorly water-soluble” means a property that the solubility in 100 g of ion-exchanged water at 25 ° C. is 0.06 g or less (preferably 0.04 g or less, more preferably 0.03 g or less).
The melting point (° C.) of the poorly water-soluble wax (a) is preferably from 60 to 200, more preferably from 70 to 180, and particularly preferably from 80 to 170. That is, the melting point (° C.) of (a) is preferably 60 or more, more preferably 70 or more, particularly preferably 80 or more, and preferably 200 or less, more preferably 180 or less, and particularly preferably 170 or less. is there. Within this range, the stability of the wax emulsified dispersion to heat (especially the stability over time of the wax emulsified dispersion in summer) is further improved. Further, the particle size of the emulsified and dispersed particles is more easily controlled (the heat stability is further improved by setting the particle size to an appropriate value).
[0007]
The melting point can be measured using a differential scanning calorimeter (for example, TG / DTA220U manufactured by SII). The measurement is carried out by measuring 10 mg of a sample in a sample container, and then raising the temperature from room temperature (15 to 30 ° C.) to 400 ° C. at a rate of 10 ° C. per minute in an air atmosphere. The melting point is defined as the temperature at the point where the tangent to the peak detection start point and the tangent to the inflection point of the peak curve intersect for the endothermic peak at the highest temperature position on the graph.
[0008]
Examples of the poorly water-soluble wax (a) include natural waxes and synthetic waxes. Examples of the natural wax include plant natural waxes (carnauba wax, candelilla wax, sugar wax, rice wax, wood wax, bayberry wax, ocully wax and esparto wax, etc.), animal wax (beetle wax, insect wax, whale wax, Shellac wax and lanolin wax, etc., petroleum natural wax (montan wax, paraffin wax, microcrystalline wax, etc.), mineral oil natural wax (ozokerite wax, ceresin, etc.) and the like are used. Among them, vegetable natural wax, petroleum natural wax and mineral oil natural wax are preferred, and carnauba wax, montan wax, paraffin wax, microcrystalline wax and ozokerite wax are more preferred.
[0009]
Synthetic waxes include oxidized natural wax, amide wax, polyethylene wax, oxidized polyethylene wax, acid-modified polyethylene wax, polypropylene wax, acid-modified polypropylene wax, acid-modified polypropylene wax, Fischer-Tropsch wax, ethylene-vinyl acetate copolymer and ethylene. -(Meth) acrylic acid copolymer or the like is used. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid.
[0010]
As the oxidized natural wax, those obtained by oxidizing the above-described natural wax by air oxidation and / or ozone oxidation (introducing a carboxy group, a hydroxyl group, and / or a formyl group) can be used. Of these, from the viewpoints of easiness of emulsification dispersion of the wax emulsified dispersion and stability over time, etc., oxidized petroleum natural wax or oxidized mineral oil natural wax obtained by oxidizing petroleum natural wax or mineral oil natural wax is preferable, and further more preferable. Is an oxide of paraffin wax, microcrystalline wax or ozokerite wax. Further, the acid value (mgKOH / g) of the oxidized natural wax is preferably from 0.1 to 50, more preferably from 0.5 to 45, particularly preferably from the viewpoint of the stability of the emulsified dispersion over time and the stability of dilution with water. Preferably it is 1-40. That is, the acid value (mgKOH / g) of the oxidized natural wax is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1 or more, and is preferably 50 or less, more preferably 45 or less. And particularly preferably 40 or less.
In addition, in this invention, an acid value means the value measured based on JISK2501-1996. The measurement sample is dissolved in the titration solvent by heating (75 ± 5 ° C.).
[0011]
Examples of the amide wax include fatty acid monoamides having 6 to 20 carbon atoms (hexyl amide, lauryl amide, stearyl amide, eicosyl amide, etc.), and fatty acid diamides having 14 to 38 carbon atoms (ethylene bishexyl amide, ethylene bis stearyl amide, and ethylene bis amide). Lauryl amide, etc.) can be used. Of these, amides having 18 to 38 carbon atoms are preferred, and stearyl amide, ethylene bislauryl amide and ethylene bis stearyl amide are more preferred.
[0012]
Examples of the polyethylene wax include those obtained by polymerization of ethylene, those obtained by thermal decomposition (low molecular weight reduction) of polyethylene for general molding, and those obtained by separation and purification of low molecular weight polyethylene by-produced in producing polyethylene for general molding. Some of them can be used, but those obtained by any method can be used.
The weight average molecular weight (Mw) of the polyethylene wax is preferably from 500 to 10,000, more preferably from 600 to 9,000, particularly preferably from the viewpoint of the stability of the emulsified dispersion over time and the ease of emulsified dispersion. 700-8,000. That is, the Mw of the polyethylene wax is preferably at least 500, more preferably at least 600, particularly preferably at least 700, preferably at most 10,000, more preferably at most 9,000, particularly preferably at 8,000. It is as follows. The weight average molecular weight (Mw) was measured using a static light scattering photometer {for example, a static light scattering photometer SLS-6000 manufactured by Otsuka Electronics Co., Ltd.) with a solvent of 1-chloronaphthalene and a measurement temperature of 160 ° C. Measured (the same applies hereinafter).
[0013]
As the oxidized polyethylene wax, those obtained by oxidizing the above-described polyethylene wax by air oxidation and / or ozone oxidation (introducing a carboxy group, a hydroxyl group, and / or a formyl group) can be used. The Mw of the oxidized polyethylene wax is preferably in the same range as that of the polyethylene wax from the same viewpoint as that of the polyethylene wax.
Further, the acid value (mgKOH / g) of the oxidized polyethylene wax is preferably from 0.1 to 50, more preferably from 0.5 to 45, particularly preferably from the viewpoint of the stability of the emulsified dispersion over time and the stability of dilution with water. Preferably it is 1-40. That is, the acid value of the oxidized polyethylene wax is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1 or more, and preferably 50 or less, more preferably 45 or less, and particularly preferably 40 or less. It is as follows.
[0014]
As the acid-modified polyethylene wax, a carboxylic acid-modified polyethylene obtained by grafting an unsaturated double bond-containing carboxylic acid (such as α, β-unsaturated monocarboxylic acid and α, β-unsaturated dicarboxylic acid) or the like to the above polyethylene wax. Wax or the like can be used.
Examples of the α, β-unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, and 2-ethylacrylic acid.
Examples of the α, β-unsaturated dicarboxylic acid include maleic acid, maleic anhydride, malonic acid, succinic acid, itaconic acid and fumaric acid.
The Mw of the acid-modified polyethylene wax is preferably in the same range as that of the polyethylene wax from the same viewpoint as that of the polyethylene wax.
The acid value (mgKOH / g) of the acid-modified polyethylene wax is preferably from 0.1 to 50, more preferably from 0.5 to 45, particularly preferably from the viewpoints of the stability of the emulsified dispersion over time and the stability of dilution with water. Is 1 to 40. That is, the acid value of the acid-modified polyethylene wax is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1 or more, and preferably 50 or less, more preferably 45 or less, and particularly preferably. 40 or less.
[0015]
Examples of the polypropylene wax include those obtained by polymerization of propylene, those obtained by thermal decomposition (low molecular weight reduction) of polypropylene for general molding, and separation and purification of low molecular weight polypropylene produced as a by-product when producing polypropylene for general molding. Some are obtained, but those obtained by any method can be used.
The Mw of the polypropylene wax is preferably from 1,000 to 50,000, more preferably from 1,500 to 40,000, particularly preferably from 2,500, from the viewpoints of the stability over time of the emulsified dispersion and the ease of emulsification and dispersion. 3,000 to 30,000. That is, Mw of the polypropylene wax is preferably 1,000 or more, more preferably 1,500 or more, particularly preferably 2,000 or more, and preferably 50,000 or less, more preferably 40,000 or less, Particularly preferably, it is 30,000 or less.
[0016]
As the oxidized polypropylene wax, those obtained by oxidizing the above-mentioned polypropylene wax by air oxidation and / or ozone oxidation (introducing a carboxy group, a hydroxyl group and / or a formyl group), and the like can be used.
The Mw of the oxidized polypropylene wax is preferably in the same range as that of the polypropylene wax from the same viewpoint as in the case of the polypropylene wax.
The acid value (mgKOH / g) of the oxidized polypropylene wax is preferably from 0.1 to 50, more preferably from 0.5 to 45, and particularly preferably from the viewpoints of the stability of the emulsified dispersion over time and the stability of dilution with water. 1 to 40. That is, the acid value of the oxidized polypropylene wax is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1 or more, and is preferably 50 or less, more preferably 45 or less, and particularly preferably 40 or less. It is as follows.
[0017]
As the acid-modified polypropylene wax, a carboxylic acid-modified polypropylene obtained by grafting an unsaturated double bond-containing carboxylic acid (such as α, β-unsaturated monocarboxylic acid and α, β-unsaturated dicarboxylic acid) or the like to the above polypropylene wax. Wax or the like can be used.
The Mw of the acid-modified polypropylene wax is preferably in the same range as the polypropylene wax from the same viewpoint as in the case of the polypropylene wax.
The acid value (mgKOH / g) of the acid-modified polypropylene wax is preferably from 0.1 to 50, more preferably from 0.5 to 45, particularly preferably from 1 to 40, from the viewpoint of the stability of the emulsified dispersion with time. is there. That is, the acid value of the acid-modified polypropylene wax is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1 or more, and preferably 50 or less, more preferably 45 or less, and particularly preferably. 40 or less.
[0018]
Fischer-Tropsch wax is obtained by distilling a product obtained from the coal-based gas by the Ager method and hydrogenating this high-boiling fraction, manufactured by Sasol Corporation of South Africa. Is preferred. Mw of the Fischer-Tropsch wax is preferably from 450 to 1,700, more preferably from 500 to 1,600, particularly preferably from 600 to 1, from the viewpoints of temporal stability of the emulsified dispersion and easiness of emulsification and dispersion. 500. That is, Mw of the Fischer-Tropsch wax is preferably 450 or more, more preferably 500 or more, particularly preferably 600 or more, and preferably 1,700 or less, more preferably 1,600 or less, particularly preferably 1,600 or less. 500 or less.
[0019]
As the ethylene-vinyl acetate copolymer, those obtained by copolymerization of ethylene and vinyl acetate (emulsion polymerization, bulk polymerization, solution polymerization, or the like) can be used.
The content (% by weight) of the vinyl acetate unit in the ethylene-vinyl acetate copolymer is based on the weight of the ethylene-vinyl acetate copolymer from the viewpoint of the stability over time of the emulsified dispersion and the stability of dilution with water. , 1 to 40, more preferably 2 to 30, particularly preferably 3 to 25. That is, the content (% by weight) of vinyl acetate in the ethylene-vinyl acetate copolymer is preferably 1 or more, more preferably 2 or more, particularly preferably 3 or more, and preferably 40 or less, more preferably Is 30 or less, particularly preferably 25 or less.
The content (% by weight) of the ethylene unit in the ethylene-vinyl acetate copolymer is determined based on the weight of the ethylene-vinyl acetate copolymer from the viewpoint of the stability over time of the emulsified dispersion and the stability of dilution with water. It is preferably from 60 to 99, more preferably from 70 to 98, particularly preferably from 75 to 97. That is, the content (% by weight) of ethylene in the ethylene-vinyl acetate copolymer is preferably 60 or more, more preferably 70 or more, particularly preferably 75 or more, and preferably 99 or less, and more preferably 99 or less. It is 98 or less, particularly preferably 97 or less.
The Mw of the ethylene-vinyl acetate copolymer is preferably from 2,000 to 50,000, more preferably from 2,500 to 40,000, from the viewpoint of the stability over time of the emulsified dispersion and the ease of emulsification and dispersion. 000, particularly preferably 3,000 to 30,000. That is, Mw of the ethylene-vinyl acetate copolymer is preferably 2,000 or more, more preferably 2,500 or more, particularly preferably 3,000 or more, and preferably 50,000 or less, more preferably 50,000 or less. It is 40,000 or less, particularly preferably 30,000 or less.
[0020]
As the ethylene- (meth) acrylic acid copolymer, those obtained by copolymerization of ethylene and (meth) acrylic acid (emulsion polymerization, bulk polymerization, solution polymerization, or the like) can be used.
The content (% by weight) of the (meth) acrylic acid unit in the ethylene- (meth) acrylic acid copolymer is determined based on the stability of the emulsified dispersion over time and the stability of dilution with water. It is preferably from 1 to 30, more preferably from 2 to 28, and particularly preferably from 3 to 25, based on the weight of the acid copolymer. That is, the content (% by weight) of the (meth) acrylic acid unit in the ethylene- (meth) acrylic acid copolymer is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. It is preferably 30 or less, more preferably 28 or less, and particularly preferably 25 or less.
The content (% by weight) of ethylene units in the ethylene- (meth) acrylic acid copolymer is determined from the viewpoint of the stability of the emulsified dispersion over time and the stability of dilution with water. It is preferably from 70 to 99, more preferably from 72 to 98, and particularly preferably from 75 to 97, based on the weight of. That is, the content (% by weight) of ethylene units in the ethylene- (meth) acrylic acid copolymer is preferably 70 or more, more preferably 72 or more, particularly preferably 75 or more, and preferably 99 or less. , More preferably 98 or less, particularly preferably 97 or less.
[0021]
The Mw of the ethylene- (meth) acrylic acid copolymer is preferably from 2,000 to 50,000, more preferably from 2,500, from the viewpoint of the stability over time of the emulsified dispersion and the ease of emulsification and dispersion. It is 40,000, particularly preferably 3,000 to 30,000. That is, Mw of the ethylene- (meth) acrylic acid copolymer is preferably 2,000 or more, more preferably 2,500 or more, particularly preferably 3,000 or more, and preferably 50,000 or less, It is more preferably at most 40,000, particularly preferably at most 30,000.
[0022]
Among these synthetic waxes, polyethylene oxide wax, acid-modified polypropylene wax and ethylene-vinyl acetate copolymer are preferred, and polyethylene oxide wax and acid-modified polypropylene wax are more preferred.
These natural waxes and synthetic waxes may be used alone or in combination of two or more.
[0023]
As the hardly water-soluble metal soap (b), any hardly water-soluble metal soap can be used without limitation. However, fatty acid alkali metal salts (such as sodium and potassium) and fatty acid ammonium salts form micelles in water and dissolve. In addition, since it is difficult to form composite particles with the poorly water-soluble wax (a), the desired substrate surface modifying ability cannot be sufficiently exhibited, which is not preferable.
The poorly water-soluble metal soap (b) includes a metal carboxylate having 8 to 38 carbon atoms.
Examples of the carboxylic acid having 8 to 38 carbon atoms include saturated fatty acids (caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachinic acid, behenic acid, montanic acid, etc.), unsaturated fatty acids (octenoic acid, Tetradecenoic acid, hexadecenoic acid, oleic acid, elaidic acid, erucic acid, stearolic acid, linoleic acid, linolenic acid, etc., oxycarboxylic acids (12-hydroxystearic acid, ricinoleic acid, etc.), alicyclic carboxylic acids (Alepress Formic acid, alepic acid, α-cyclohexyl stearic acid and gorlic acid, etc., aromatic carboxylic acids (γ-phenylbutyric acid, δ-phenylvaleric acid, ε-phenylcaproic acid, etc.), dibasic acids (azeleic acid, sebacic acid) And a dimer of oleic acid).
[0024]
In addition, fatty acids obtained from natural fats and oils which are a mixture of these can also be used. Natural fats and oils include plant-derived fats and oils (linseed oil, olive oil, cocoa butter, sesame oil, rice bran oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, Cottonseed oil and coconut oil) and animal-derived fats and oils (such as beef tallow, lard, milk fat, fish fat, and whale oil).
Among these carboxylic acids, lauric acid, myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, oleic acid, 12-hydroxystearic acid, dimer of oleic acid, fatty acids derived from tallow and fatty acids derived from coconut oil are preferred. . Further, each of the carboxylic acids may be used alone, or a plurality of carboxylic acids may be used in any combination.
[0025]
Examples of the metal salt include metals belonging to Group 2 of the periodic table (such as magnesium, calcium, zinc and barium), metals belonging to Groups 8 to 12 (such as iron, cobalt, nickel and zinc), and metals belonging to Group 13 of the periodic table. Salts of metals (such as aluminum) can be used. Among these metal salts, salts of metals belonging to Group 2 of the periodic table, metals of Group 12 or metals of Group 13 are preferable, and magnesium salts, calcium salts, zinc salts and aluminum salts are more preferable.
[0026]
The content weight ratio (a / b) of the poorly water-soluble wax (a) and the poorly water-soluble metal soap (b) is preferably 0.04 to 4, more preferably 0.05 to 3, and particularly preferably 0.08 to 3. 2.5. That is, the content weight ratio (a / b) of (a) and (b) is preferably 0.04 or more, more preferably 0.05 or more, particularly preferably 0.08 or more, and 4 or less. Is more preferable, more preferably 3 or less, particularly preferably 2.5 or less. When it is in this range, the substrate surface modifying ability is further improved.
[0027]
The wax-metal soap composite emulsified dispersion of the present invention only needs to contain composite particles in which the poorly water-soluble wax (a) and the poorly water-soluble metal soap (b) are contained in one particle. Even if (a) and (b) in them are melted (dissolved) and uniform, or the particles composed of (a) and the particles composed of (b) are adsorbed to form an aggregate. The particles of (a) or the particles of (b) may be coated with the other (b) or (a). Of these, the particles of (a) or (b) are coated with the other (b) or (a), and the particles of (a) and the particles of (b) adsorb each other. It is preferable that the particles are composed of an aggregate, and more preferably the particles composed of (a) and the particles composed of (b) are adsorbed to form an aggregate.
[0028]
When the particles of (a) or (b) are coated with the other {(a) or (b)}, the coating layer preferably has a thickness (μm) of 0.01 to 20, more preferably 0.1 to 20 μm. 02-18, particularly preferably 0.05-15. That is, in this case, the thickness (μm) of the coating layer is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.05 or more, and preferably 20 or less, more preferably 18 or less. Or less, particularly preferably 15 or less. When it is in this range, the substrate surface modifying ability is further improved.
[0029]
When the particles composed of (a) and the particles composed of (b) are adsorbed to form an aggregate, the particle diameter (μm) of the particles composed of (a) is preferably 0.01 to 20, and furthermore It is preferably from 0.02 to 18, particularly preferably from 0.05 to 15. The particle diameter (μm) of the particles (b) is preferably 0.01 to 20, more preferably 0.02 to 18, and particularly preferably 0.05 to 15. That is, in this case, the particle diameter (μm) of the particles composed of (a) or the particles composed of (b) is preferably 0.01 or more, more preferably 0.02 or more, and particularly preferably 0.05 or more. Yes, and preferably 20 or less, more preferably 18 or less, and particularly preferably 15 or less. When the particle diameter is within this range, the substrate surface modifying ability is further improved.
[0030]
The shape of the composite particles of the poorly water-soluble wax (a) and the poorly water-soluble metal soap (b) contained in the wax-metal soap composite emulsified dispersion of the present invention may be spherical, plate-like, needle-like, square, irregular, etc. Any shape may be used, but a spherical shape is preferred from the viewpoint of the stability over time of the emulsified dispersion.
[0031]
When the hardly water-soluble wax (a) and the hardly water-soluble metal soap (b) are uniform in the composite particles, (a) and (b) are compatible with each other to make the entire composite particles uniform. (A) or (b) as a main body, and a sea-island structure in which the other (b) or (a) is scattered, and (a) from the center of the composite particle toward the surface. ) And (b) may have any gradient. Among them, in order to more effectively exhibit the substrate surface modifying ability, a sea-island structure in which (a) or (b) is the main component and the other (b) or (a) is scattered therein And those having a gradient in the mixing ratio of (a) and (b) from the center of the composite particle toward the surface.
[0032]
When the composite particles adsorb particles of the poorly water-soluble wax (a) and particles of the poorly water-soluble metal soap (b) to form an aggregate, the particles of (a) and the particles of (b) Are agglomerated with each other to form one particle in the form of a mixture of each of them, or one of the particles consisting of (a) or the particles consisting of (b) as a nucleus, and the other ( Any of particles having the core-shell structure in which the particles of b) or particles of (a) are aggregated, and those having a layered structure in which the other particles are repeatedly aggregated outside the core-shell structure may be used. Among these, those having a core-shell structure or a layered structure are preferable in order to more effectively exhibit the substrate surface modifying ability.
[0033]
When the composite particles are coated with the particles of the poorly water-soluble wax (a) or the particles of the poorly water-soluble metal soap (b) and the other (b) or (a), the particles of the particles (a) or (b) Either one having a core-shell structure in which one surface is coated with the other (b) or (a) and the other having a layered structure in which the other is repeatedly coated on the outside of the core-shell structure, etc. May be. Among these, those having a core-shell structure or a layered structure are preferable in order to more effectively exhibit the substrate surface modifying ability.
[0034]
The wax-metal soap composite emulsified dispersion of the present invention contains an emulsified dispersion medium. As the emulsifying dispersion medium, any aqueous liquid can be used without limitation, and water (industrial water, tap water and deionized water), an aqueous solution comprising water and a water-soluble solvent, and the like can be used.
Examples of the water-soluble solvent include organic liquids having a solubility of 3 or more in 100 g of water at 25 ° C, alcohols having 1 to 5 carbon atoms (such as methanol, ethanol, propanol, ethylene glycol and glycerin), and carbon atoms having 1 to 5 carbon atoms. 5 ketones (such as acetone, methyl ethyl ketone, dioxane and tetrahydrofuran), esters having 2 to 4 carbon atoms (such as methyl formate, methyl acetate and ethyl acetate), and other solvents (2-ethoxyethanol, 2-butoxyoxyethanol, -Phenoxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethyl cellosolve, butyl cellosolve and the like). The content ratio of the water-soluble solvent to water in the aqueous solution comprising water and the water-soluble solvent (water-soluble solvent / water) is preferably 0.6 or less, more preferably 0.1 or less, and particularly preferably. 0.05 or less.
Of these, water is preferred, and tap water and deionized water are more preferred.
[0035]
The pH of the emulsifying dispersion medium (such as water and aqueous solution) is preferably 5 to 12, more preferably 5.5 to 10, and particularly preferably 6 to 8. That is, the pH of the emulsifying dispersion medium is preferably 5 or more, more preferably 5.5 or more, particularly preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. . When the pH is in this range, the stability over time (aggregation, separation, gelation, thickening, etc.) of the emulsified dispersion is further improved. The pH was measured at a measurement temperature of 25 using a glass electrode type pH meter using a silver / silver chloride electrode {for example, Castani LAB pH meter manufactured by Horiba Ltd.) in accordance with JIS K0802-1996. Measured as ° C.
[0036]
The pH of the emulsifying dispersion medium can be adjusted by passing through a cation exchange resin or an anion exchange resin, and can also be adjusted by adding an appropriate acid or base. The acid is preferably a strong acid such as hydrochloric acid, sulfuric acid and nitric acid, and more preferably hydrochloric acid and sulfuric acid. As the base, ammonia, monoethanolamine, diethanolamine, triethanolamine, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable, and ammonia, sodium hydroxide and potassium hydroxide are more preferable.
[0037]
The content (% by weight) of the poorly water-soluble wax (a) and the poorly water-soluble metal soap (b) in the wax-metal soap composite emulsified dispersion of the present invention is the sum of (a), (b) and the emulsified dispersion medium. Based on the weight, it is preferably 0.5 to 70, more preferably 1.0 to 65, and particularly preferably 3.0 to 60. That is, the content (% by weight) of (a) and (b) is preferably 0.5 or more, more preferably 1.0 based on the total weight of (a), (b) and the emulsifying dispersion medium. As mentioned above, it is particularly preferably at least 3.0, more preferably at most 70, further preferably at most 65, particularly preferably at most 60. When the content of (a) and (b) is in this range, the stability over time (particularly, cohesiveness and separability) of the emulsified dispersion is further improved.
[0038]
The content (% by weight) of the emulsifying dispersion medium is preferably 30 to 95, more preferably 35 to 93, based on the total weight of the hardly water-soluble wax (a), the hardly water-soluble metal soap (b) and the emulsifying dispersion medium. Particularly preferably, it is 40 to 90. That is, the content (% by weight) of the emulsifying dispersion medium is preferably 30 or more, more preferably 35 or more, and particularly preferably 40 or more, based on the total weight of (a), (b) and the emulsifying dispersion medium. Also, it is preferably 95 or less, more preferably 93 or less, particularly preferably 90 or less. Within this range, the stability over time (aggregation and separation, etc.) of the emulsified dispersion will be further improved.
[0039]
When the poorly water-soluble wax (a) has a carboxy group, the emulsified dispersion of the present invention may further contain a base. When a base is contained, the ease of producing the emulsified dispersion and the stability over time are further improved.
When a base is contained, the content (molar equivalent) of the base is preferably 0.05 to 3, more preferably 0.2 to 2, and particularly preferably 0.2, per molar equivalent of the total carboxy groups of the poorly water-soluble wax (a). Is 0.3 to 1. That is, in this case, the content (molar equivalent) of the base is preferably 0.05 or more, more preferably 0.2 or more, particularly preferably 0.3 or more, per molar equivalent of the carboxy group contained in (a). And preferably 3 or less, more preferably 2 or less, particularly preferably 1 or less. When the content of the base is in this range, the stability over time (aggregation, separation, gelation, thickening, and the like) of the emulsified dispersion is further improved.
[0040]
As the base, any base can be used as long as it is strong enough to neutralize the carboxy group, and includes ammonia, amines, metal salts and the like.
As the amine, an alkylamine, an alkanolamine, an aromatic amine, a polyamine and the like can be used.
As the alkylamine, a mono-, di- or tri-alkylamine having 1 to 22 carbon atoms is used, and methylamine, ethylamine, triethylamine, butylamine, dibutylamine, tributylamine, methylbutylamine, decylamine, cyclohexylamine, cyclohexyl Examples include methylamine, dicyclohexylamine, allylamine, 2-ethylhexylamine, dodecylamine, octadecylamine, octadecenylamine, morpholine and piperidine.
[0041]
As the alkanolamine, a mono-, di- or tri-alkanolamine having 2 to 22 carbon atoms is used, and monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-methylaminoethanol, 2- (diethylamino ) Ethanol and 3-hydroxypropylamine.
[0042]
As the aromatic amine, an aromatic mono-, di- or tri-amine having 6 to 22 carbon atoms is used, and aniline, pyridine, pyrrole, benzylamine, methylbenzylamine, N-methylaniline, N, N- Examples include dimethylaniline, N, N-diethylaniline, toluidine, quinoline, isoquinoline, picoline, lutidine and the like.
[0043]
Examples of the polyamine include alkylene polyamines having 2 to 22 carbon atoms {such as ethylene diamine, propylene diamine and hexylene diamine}, arylene polyamines having 6 to 22 carbon atoms {such as phenylenediamine and 1,4-naphthalenediamine} and 4 to 4 carbon atoms. For example, 22 polyethylene polyamines (such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine) are used.
[0044]
As the metal salt, a metal hydroxide or the like can be used, and metals of Group 1 of the periodic table (such as lithium, sodium and potassium), metals of Group 2 (such as magnesium and calcium), and Groups 8 to 12 of the element (Iron, cobalt, nickel, etc.) or hydroxides of the same Group 13 metals (aluminum, etc.).
Of these bases, ammonia, alkanolamines and metal salts are preferred, more preferably ammonia, alkanolamines and metal hydroxides, particularly preferably ammonia, monoethanolamine, diethanolamine, triethanolamine, lithium hydroxide, hydroxide Sodium and potassium hydroxide. These bases may be used alone or in any combination.
[0045]
During the production and storage of the emulsified dispersion of the present invention, to prevent separation, sedimentation and generation of aggregates, or to prevent a significant change in the viscosity of the emulsified dispersion or the volume average particle diameter of the composite particles, The emulsified dispersion of the present invention may further contain a surfactant and / or a water-soluble polymer.
[0046]
The surfactant is not particularly limited as long as it can emulsify and disperse the hardly water-soluble wax (a) and the hardly water-soluble metal soap (b) in the emulsifying dispersion medium. Known nonionic surfactants and anionic surfactants Surfactants, cationic surfactants and amphoteric surfactants can be used. Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene castor oil fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester, diglycerin fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, polyglycerin Condensed ricinoleate, modified polyether silicone, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkyl phenyl ether , Polyoxyethylene propylene alkyl phenyl ether, polyoxyethylene fatty acid ester, Lioxyethylene benzyl ester, polyoxyethylene castor oil ether, polyoxyethylene hardened castor oil ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyethylene glycol fatty acid ester , Fatty acid alkanolamides and polyoxyethylene polyoxypropylene glycol.
[0047]
Examples of the anionic activator include alkyl ether sulfates, sulfated oils, sulfated fatty acid esters, alkylbenzene sulfonates, alkane sulfonates, α-olefin sulfonates, alkyl sulfosuccinates, dialkyl sulfosuccinates, and polyalkyl sulfonates. Oxyethylene alkyl ether / sulfosuccinic acid partial ester salt, polyoxyethylene alkyl sulfate, higher alcohol sulfate, aliphatic monocarboxylate, polyoxyalkyl ether carboxylate, N-acyl sarcosine, N-acylglutamic acid Salt, naphthalene sulfonate, naphthalene sulfonate-formaldehyde condensate, alkyl naphthalene sulfonate, N-methyl-N-acyl taurate, alkyl phosphate, polyoxyethylene alkyl ether Phosphates and polyoxyethylene alkylphenyl phosphates and the like are mentioned, and as salts, ammonia salts, alkylamine (such as monoethylamine, monobutylamine and triethylamine) salts and alkanolamines (monoethanolamine, diethanolamine and triethanolamine) And the like, and amine salts such as salts, and salts of Group 1 metals (such as lithium, sodium and potassium) and salts of Group 2 metals (such as magnesium, calcium and zinc) of the periodic table.
[0048]
Examples of the cationic surfactant include a monoalkylamine salt, a dialkylamine salt, a trialkylamine salt, an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, and an alkylbenzyldimethylammonium salt. And iodine), halogen oxides (such as chlorous acid, perchloric acid, perfluoric acid and periodate), nitrogen oxides, sulfur oxides, phosphorus oxides, and metals of Group 13 of the Periodic Table of the Elements. Oxides (aluminic acid, titanic acid, tungstic acid, etc.) and the like can be mentioned.
[0049]
Examples of the amphoteric surfactant include alkyl betaine, fatty acid amidopropyl betaine, 2-alkyl-N-carboxylmethyl-N-hydroxyethyl-imidazolinium betaine, alkyldiethylenetriaminoacetic acid, dialkyldiethylenetriaminoacetic acid, and alkylamine oxide. Can be
[0050]
As the water-soluble polymer, known water-soluble polymers and the like can be used, and natural polymers (cellulose, pullulan, sodium alginate, gum arabic, guar gum, carrageenan, gelatin, curdlan, agar, starch, xanthan gum, welan gum, ramzan gum) , Tragacanth gum, carob gum, locust bean gum, pectin, dextran, casein, albumin and agarose, etc., semi-synthetic polymers (methylcellulose, ethylcellulose, nitrocellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, cellulose sodium sulfate, carboxymethylethylcellulose) , Carboxymethyl starch and propylene glycol alginate), synthetic polymers ｛polyvinyl alcohol , Polyethylene oxide, polyoxyethylene propylene copolymer, polyacrylamide, polymethacrylamide, polyvinylpyrrolidone, poly (meth) acrylic acid (salt), polystyrenesulfonic acid (salt), naphthalenesulfonic acid formalin condensate (salt), (Meth) acrylamide and (meth) acrylic acid copolymer (salt), (meth) acrylic acid and maleic acid copolymer (salt), styrene and maleic acid copolymer (salt), styrene and (meth) ) Acrylic acid copolymer (salt). Examples of the salt include amine salts such as ammonia salt, alkylamine (monoethylamine, monobutylamine, triethylamine, etc.) salt and alkanolamine (monoethanolamine, diethanolamine, triethanolamine, etc.) salt, Periodic Table 1 of the Elements. Group 2 metal (such as lithium, sodium and potassium) salts and Group 2 metal (such as magnesium, calcium and zinc) salts, etc., may be completely or partially salted.
[0051]
When a plurality of these surfactants and / or water-soluble polymers are used in combination, the same ionicity is combined from the viewpoint of prevention of aggregation and separation of the emulsified dispersion of the present invention, and nonionic properties are combined. And combinations of nonionic and other ionics are preferred.
[0052]
When a surfactant and / or a water-soluble polymer is contained, the content (% by weight) is preferably less than 50 based on the total weight of the hardly water-soluble wax (a) and the hardly water-soluble metal soap (b), It is more preferably less than 30, particularly preferably less than 20. Within this range, it is possible to suppress the adverse effect of the emulsified dispersion on the substrate surface modifying ability.
[0053]
The emulsified dispersion of the present invention may further contain additives. Additives include antioxidants, ultraviolet absorbers, water-proofing agents, antifouling agents, antistatic agents, viscosity adjusters, pH adjusters, penetrants, leveling agents, crosslinkers, antiseptic and fungicides, bactericides, Antifoams, fragrances, dyes and pigments are included. When the additive is contained, the content (% by weight) is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less, based on the weight of the emulsified dispersion.
[0054]
The volume average particle diameter (μm) of the composite particles in the wax-metal soap composite emulsified dispersion of the present invention (volume average particle diameter measured by a laser diffraction type particle size distribution analyzer) is preferably 0.01 to 60, and more preferably. 0.02 to 45, particularly preferably 0.03 to 40. That is, the volume average particle diameter (μm) of the composite particles is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.03 or more, and preferably 60 or less, more preferably 45 or less. Or less, particularly preferably 40 or less. When the volume average particle diameter of the composite particles is in this range, the stability over time (viscosity, cohesiveness, and separability) of the emulsified dispersion is further improved.
[0055]
When the volume average particle size is larger than 1 μm, the volume average particle size is measured by a laser diffraction type particle size analyzer [for example, Microtrac HRA particle size analyzer manufactured by Nikkiso Co., Ltd.] (dispersion medium: deionized water, Measurement temperature: 25 ° C). Those having an average particle size smaller than 1 μm are measured by a laser Doppler type particle size analyzer [for example, Microtrac UPA particle size analyzer manufactured by Nikkiso Co., Ltd.] (dispersion medium: deionized water, measurement temperature: 25 ° C.) ).
[0056]
The method for producing the emulsified dispersion of the present invention is not particularly limited. (1) A method of preliminarily melt-mixing a hardly water-soluble wax (a) and a hardly water-soluble metal soap (b), and emulsifying and dispersing the melt mixture. (2) A method of emulsifying and dispersing (a) and then emulsifying and dispersing (b) in the emulsifying dispersion of (a); (3) Emulsifying and dispersing (b) and then emulsifying and dispersing (b) (4) a method in which (a) is emulsified and dispersed in the body, (4) a method in which a part of (a) and (b) is emulsified and dispersed, and then a remaining (b) is emulsified and dispersed, and (5) (b) And a method in which a part of (a) is emulsified and dispersed, and then the remaining (a) is emulsified and dispersed. (6) The emulsified dispersion of (a) and the emulsified dispersion of (b) are separately produced, A mixing method or the like can be applied.
[0057]
In the methods (2), (3), (5) and (6), the method of emulsifying and dispersing the poorly water-soluble wax (a) is as follows: (a) is carried out in the presence of a surfactant and / or a water-soluble polymer. , A method of dispersing in an emulsifying dispersion medium with a stirring mixer or an emulsifying disperser, or in the same manner as described in JP-A-2002-69302, JP-A-2002-69302 or JP-A-6-136304. , An emulsifying dispersion medium, (a), a base, a surfactant, and / or a water-soluble polymer are placed in a reaction vessel, heated to a temperature equal to or higher than the melting point of (a), emulsified and dispersed by a stirring mixer or an emulsifying disperser, and then cooled. And the like. In the cases of (3) and (5), an emulsified dispersion of a sparingly water-soluble metal soap (b) or an emulsified dispersion of a sparingly water-soluble wax (a) and a sparingly water-soluble metal soap (b) instead of the emulsifying dispersion medium. Is used.
[0058]
In the methods (2), (3), (4) and (6), the method of emulsifying and dispersing the poorly water-soluble metal soap (b) is as follows: (b) is the presence of a surfactant and / or a water-soluble polymer. Below, a method of dispersing in an emulsifying dispersion medium by a stirring mixer or an emulsifying and dispersing machine, or the emulsifying dispersion medium, (b), a base, a surfactant and / or a water-soluble polymer are put in a reaction vessel, and the melting point of (b) A method of heating, emulsifying and dispersing with a stirring mixer or an emulsifying and dispersing machine and then cooling, and a known melting method, semi-melting method or double decomposition method (for example, JP-B-63-57414, JP-A-58-12267) And JP-A-1-35745). In the cases of (2) and (4), an emulsified dispersion of a sparingly water-soluble wax (a) or an emulsified dispersion of a sparingly water-soluble wax (a) and a sparingly water-soluble metal soap (b) is used instead of the emulsifying dispersion medium. .
[0059]
In the methods (1), (4) and (5), after preliminarily melt-mixing the poorly water-soluble wax (a) and the poorly water-soluble metal soap (b), the resulting melt mixture is emulsified and dispersed. It is preferably at least the highest melting point of (a) and (b) used, more preferably at least 10 ° C higher than the highest melting point, particularly preferably at least 15 ° C higher than the highest melting point. The temperature is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, particularly preferably 220 ° C. or lower. In addition, as a method of emulsifying and dispersing a molten mixture composed of the hardly water-soluble wax (a) and the hardly water-soluble metal soap (b), the same method as described above can be applied.
[0060]
In the method of (6), the emulsified dispersion of the poorly water-soluble wax (a) and the emulsified dispersion of the poorly water-soluble metal soap (b) are mixed in an arbitrary order. After mixing, a method of mixing using a known stirring mixer, a method of mixing while gradually adding each emulsified dispersion to a mixing container, and a method of mixing one of the emulsified dispersions in a mixing container A method of mixing while gradually adding the other emulsified dispersion can be applied. The mixing temperature is preferably at least the lowest melting point among the melting points of (a) and (b) used, more preferably at least 10 ° C. higher than the lowest melting point, particularly preferably at least the lowest melting point. Further, the temperature is higher by 15 ° C. or higher, and preferably 250 ° C. or lower, more preferably 230 ° C. or lower, particularly preferably 220 ° C. or lower. Further, as the stirring mixer, an impeller-type stirrer (propeller-type blade stirrer, paddle-type blade stirrer and turbine-type blade stirrer), a kneader, a line mixer, a planetary mixer, and the like can be used.
[0061]
In order to make the composite particles uniform by melting (dissolving) the composite particles (a) and (b), the method (1) is preferable.
In order for the composite particles to adsorb the particles composed of (a) and the particles composed of (b) to form an aggregate, the methods (2) to (6) are preferable, and more preferably (2) and (3). ▼ and ６, particularly preferably ６. In the method (6), the stirring peripheral speed (m / min) of the stirring mixer is preferably from 30 to 500, more preferably from 50 to 300. When the stirring peripheral speed is in this range, the emulsified dispersion can be produced more efficiently without dissociating the aggregate again.
For the purpose of promoting the aggregation of the particles and improving the stability of the aggregate, it is preferable to adjust the pH of the emulsifying dispersion medium by adding an appropriate acid or base. The acid is preferably a strong acid such as hydrochloric acid, sulfuric acid and nitric acid, and more preferably hydrochloric acid and sulfuric acid. As the base, ammonia, monoethanolamine, diethanolamine, triethanolamine, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable, and ammonia, sodium hydroxide and potassium hydroxide are more preferable. The adjustment of the pH is preferably performed immediately after the production of the emulsified dispersion from the viewpoint of the stability over time of the emulsified dispersion.
[0062]
In order to make the composite particle a particle composed of (a) or a particle composed of (b) coated with the other (b) or (a), the methods (2) to (6) can be applied. it can. In order to perform coating by these methods, it is preferable that the melting point of (b) or (a) to be coated is lower than the melting point of (a) or (b) that becomes the core particles to be coated. In order to coat using the methods (2) to (5), the core particles (a) or (b) are emulsified and dispersed in advance, and then the temperature below this melting point and the other (b) or (a) are used. ) Is adjusted to a temperature equal to or higher than the melting point, and then the other (b) or (a) is emulsified and dispersed in a molten state to coat the core particles with the other (b) or (a). it can. In order to coat by using the method (6), the particles consisting of (a) or the particles consisting of (b) which are to be core particles and the particles consisting of the other (b) which become the coating layer or (a) By aggregating the particles consisting of (a) or (b), the temperature was adjusted to a temperature lower than the melting point of (a) or (b), and to a temperature higher than the melting point of (b) or (a). Only particles having a low melting point {the other (b) or (a)} can be melted and coated. Among these methods, a method applying (2), (3) or (6) is preferable, and a method (3) or (6) is more preferable, and a method (6) is particularly preferable.
[0063]
The volume average particle diameters of the particles and the composite particles in the emulsified dispersion are as follows: I) when the molten mixture of (a) and (b) is emulsified and dispersed, (a) is emulsified and dispersed, or (b) is emulsified and dispersed. A) when mixing the emulsified dispersion of (a) and the emulsified dispersion of (b), or III) after the production of the emulsified dispersion of the present invention, a stirring mixer, a high-pressure injection-type emulsifying and dispersing machine, and a grinding-type emulsifying and dispersing machine. Alternatively, it can be adjusted by a media type emulsifying and dispersing machine or the like. That is, mainly by applying a high shearing force or a crushing force (for example, in a high-pressure injection type emulsifying and dispersing machine, a discharge pressure is increased, and in a grinding type emulsifying and dispersing machine, a gap between a rotating disk and a stationary ring is narrowed. The volume average particle diameter can be reduced (by reducing the diameter of the medium used in the media type emulsifying and dispersing machine). The adjustment can also be made by changing the processing time in each device.
[0064]
The emulsified dispersion of the present invention includes a release agent for paper coating color, an anti-scratch agent for paper coating color, a lubricant for paper coating color, a waterproofing agent for paper coating color, a surface friction coefficient modifier for paper, and a moisture proof for paper. Agents, anti-scratch agent for water-based paints, release agents for water-based paints, lubricants for water-based paints, waterproofing agents for water-based paints, anti-scratch agents for water-based inks, release agents for water-based inks, lubricants for water-based inks, water-based Waterproofing agent for ink, release agent for building materials, waterproofing agent for building materials, lubricant for paints and inks, matting agent for paints and inks, waterproofing agent for agricultural sheets, ceramics binder, flexibility imparting agent for emulsion adhesives , Latex modifier, emulsion adhesive modifier, etc. Of these, release agents for paper coating colors, abrasion inhibitors for paper coating colors, paper cores Lubricants for toting colors, waterproofing agents for paper coating colors, anti-scratch agents for water-based paints, release agents for water-based paints, lubricants for water-based paints, water-resistant agents for water-based paints, anti-scratch agents for water-based inks, water-based inks It is suitable as a release agent for water, a lubricant for aqueous inks, a waterproofing agent for aqueous inks, a releasing agent for building materials and a waterproofing agent for building materials.
[0065]
When the emulsified dispersion of the present invention is used as a release agent or lubricant for paper coating colors, the emulsified dispersion of the present invention is added at the time of paper coating color adjustment as described in JP-A-1-35745. Methods and the like can be applied. Further, when used as an anti-scratch agent or a water-proofing agent for paper coating colors, as described in JP-A-10-251992, a method of adding the emulsified dispersion of the present invention at the time of paper coating color adjustment, paper For example, a method of applying the emulsified dispersion of the present invention as a surface treatment agent can be applied. When used as a release agent, a lubricant, an anti-scratch agent or a water-resistant agent for water-based paints or water-based inks, as described in JP-A-06-136304 and JP-A-7-34030, etc. In addition, a method of adding the emulsified dispersion of the present invention during or after preparation of a water-based paint or water-based ink or a method of applying the emulsified dispersion of the present invention as a surface treatment agent for printed matter can be applied. When used as a release agent, a lubricant, an abrasion inhibitor or a waterproofing agent for building materials, as described in JP-A-2002-240018, JP-A-11-170234, etc. A method of adding the emulsified dispersion of the present invention at the time of material preparation, a method of applying the emulsified dispersion of the present invention as a surface treating agent to the surface of a substrate or a mold at the time of molding, and the emulsifying dispersion of the present invention as a surface treating agent after completion of molding A method of applying a body or the like can be applied.
[0066]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, parts mean parts by weight, and% means% by weight.
<Example 1>
Oxidized polyethylene wax (a1) {trade name: AC-6702, manufactured by Allied Signal Corp., melting point 83 ° C., acid value 17 mg / g · KOH} 36 parts, nonionic surfactant {trade name: Ionnet S-80, Sanyo Chemical Industries {2 parts, nonionic surfactant} Brand name: Brownon SR-710, manufactured by Aoki Yushi Kogyo Co., Ltd. {2 parts, sodium hydroxide} Reagent 1st grade, Wako Pure Chemical Industries, Ltd. 0.7 part and deionized water 59 .3 parts were placed in a pressure-resistant airtight container equipped with a propeller-type stirring blade, heated to 100 ° C., and then stirred and mixed at the same temperature for 3 hours. Then, a high-pressure homogenizer (pressure: 1000 kg / cm ² ) And immediately cooled to 25 ° C. or lower (20 to 25 ° C.) to obtain an emulsified dispersion of oxidized polyethylene wax (a1).
[0067]
Next, 48.5 parts of water, zinc oxide (3.1 parts, manufactured by Wako Pure Chemical Industries, 3.1 parts, carboxymethyl cellulose) were placed in a jacketed pressure vessel having one paddle-type low-speed stirrer and one Coreless-type high-speed stirrer. A paddle-type low-speed stirrer was charged with 0.65 parts of Cellogen 6A, manufactured by Daiichi Yakuhin Kogyo and 0.3 parts of polyoxyethylene lauryl ether sulfate sodium salt {sulfuric acid sodium salt of ethylene oxide 6 mol adduct of lauryl alcohol} Was stirred at a peripheral speed of 100 m / min to dissolve the carboxymethyl cellulose, and the temperature of the solution was raised to 140 ° C. and maintained at this temperature. << 18.1 parts made by Wako Pure Chemical Industries >> are dropped in 60 minutes, and 10 minutes after the completion of the dropping, cooling water (5 ° C .; the same applies hereinafter) It was passed through to obtain an emulsion dispersion of zinc stearate (b1) by cooling to 60 ° C..
[0068]
A mixing vessel was charged with 14.4 parts of an emulsified dispersion of oxidized polyethylene wax (a1) and 85.6 parts of an emulsified dispersion of zinc stearate (b1), and was placed at 25 ° C. in a paddle-type low-speed stirrer (peripheral speed: 100 m / min). And the resulting mixture was stirred for 20 minutes to obtain an emulsified dispersion 1 of the present invention.
[0069]
<Example 2>
Maleic acid-modified polypropylene wax (a2) ｛Trade name: Umex 1001, manufactured by Sanyo Chemical Industries, melting point 145 ° C., acid value 26 mg / g · KOH｝ 36 parts, nonionic surfactant ｛Trade name: Ionnet S-80, Sanyo Kasei Kogyo Co., Ltd., 2 parts, nonionic surfactant. Brand name: Brownon SR-710, Aoki Yushi Kogyo Co., Ltd., 2 parts, sodium hydroxide. Reagent 1st grade, Wako Pure Chemical Co., Ltd., 0.7 parts and deionized. 59.3 parts of water was charged into a pressure-resistant closed vessel equipped with a propeller-type stirring blade, heated to 150 ° C., and then stirred and mixed at the same temperature for 3 hours. Then, a high-pressure homogenizer (pressure: 1000 kg / cm ² ) And immediately cooled to 25 ° C. or lower (20 to 25 ° C.) to obtain an emulsified dispersion of maleic acid-modified polypropylene wax (a2).
[0070]
Then, 34.8 parts of water, 4.34 parts of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), polyoxyethylene lauryl ether and lauryl were placed in a jacketed pressure vessel having one paddle-type low-speed stirrer and one coreless high-speed stirrer. 9 mol of ethylene oxide adduct of alcohol (0.82 part) and sodium dodecylbenzenesulfonate (0.2 part) were charged, and the temperature was raised to 170 ° C. and maintained at this temperature. A paddle-type low-speed stirrer was rotated at a peripheral speed of 100 m / min. While stirring at a peripheral speed of 2500 m / min, 30.3 parts of stearic acid {manufactured by Wako Pure Chemical Industries, Ltd.} at 30 ° C. was dropped in 30 minutes, and after 10 minutes from the completion of dropping, cooling water was passed through the jacket of the reaction vessel. And cooled to 55 ° C. to obtain an emulsified dispersion of calcium stearate (b2).
[0071]
47.4 parts of an emulsified dispersion of maleic acid-modified polypropylene wax (a2) and 52.6 parts of an emulsified dispersion of calcium stearate (b2) were charged into a mixing vessel, and the mixture was stirred at 25 ° C. using a paddle-type low-speed stirrer (peripheral speed 100 m / min.). ) To obtain an emulsified dispersion 2 of the present invention.
[0072]
<Example 3>
Microcrystalline wax (a3) {trade name: Hi-Mic 1080, manufactured by Nippon Seisaku, melting point 87 ° C, (acid value almost 0 mg / g · KOH)} 23 parts, montanic acid wax (a4) {trade name: Licowax S, Clariant Japan, melting point 85 ° C, 7 parts, potassium hydroxide reagent, first grade, Wako Pure Chemical Industries, 1.2 parts, nonionic surfactant. Product name: IONET S-80, Sanyo Chemical Industries, Ltd. .5 parts, nonionic surfactant {trade name: Braunon SR-710, manufactured by Aoki Yushi Kogyo Co., Ltd.} 2.5 parts and 63.8 parts of deionized water are charged into a pressure-resistant closed vessel equipped with a propeller-type stirring blade, and up to 100 ° C. After heating, the mixture was stirred and mixed at the same temperature for 3 hours. Then, a high-pressure homogenizer (pressure: 1200 kg / cm ² ) For 30 minutes, and immediately cooled to 25 ° C. or lower (20 to 25 ° C.) to obtain an emulsified dispersion of microcrystalline wax (a3).
[0073]
Then, 74.9 parts of water, 31.4 parts of palmitic acid (manufactured by Wako Pure Chemical Industries, Ltd., 31.4 parts of potassium oleate, manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a jacketed pressure-resistant container having one paddle-type low-speed stirrer and one Coreless-type high-speed stirrer. ｝ 0.6 parts, polyoxyethylene lauryl ether２０20 mol adduct of lauryl alcohol with ethylene oxide｝ 0.5 part, 0.8 parts of sodium octyl sulfosuccinate half-ester were charged, and the temperature was raised to 150 ° C. and maintained at this temperature. 8.5 parts of a 30% aqueous dispersion of magnesium oxide {manufactured by Wako Pure Chemical Industries, Ltd.} was dropped in 50 minutes while stirring the paddle-type low-speed stirrer at a peripheral speed of 100 m / min and the high-speed stirrer at a peripheral speed of 2500 m / min. Ten minutes after the completion, cooling water was passed through the jacket of the reaction vessel and cooled to 50 ° C. to obtain an emulsified dispersion of magnesium palmitate (b3).
[0074]
A mixing vessel was charged with 75.7 parts of an emulsified dispersion of microcrystalline wax (a3) and 24.3 parts of an emulsified dispersion of magnesium palmitate (b3), and a paddle-type low-speed stirrer (peripheral speed 100 m / min) at 25 ° C. And the resulting mixture was stirred for 20 minutes to obtain an emulsified dispersion 3 of the present invention.
[0075]
<Example 4>
Mixing vessel containing 30.2 parts of emulsified dispersion of polyethylene oxide wax (a1) obtained in the same manner as in Example 1 and 69.8 parts of emulsified dispersion of calcium stearate (b2) obtained in the same manner as in Example 2. And emulsified dispersion 4 of the present invention by stirring at 25 ° C. for 20 minutes with a paddle-type low-speed stirrer (peripheral speed: 100 m / min).
[0076]
<Example 5>
64.5 parts of an emulsified dispersion of oxidized polyethylene wax (a1) obtained in the same manner as in Example 1 and 35.5 parts of an emulsified dispersion of magnesium palmitate (b3) obtained in the same manner as in Example 3 were mixed. The emulsified dispersion 5 of the present invention was obtained by charging into a container and stirring at 25 ° C. for 20 minutes with a paddle-type low-speed stirrer (peripheral speed: 100 m / min).
[0077]
<Example 6>
40.1 parts of an emulsion dispersion of maleic acid-modified polypropylene wax (a2) obtained in the same manner as in Example 2 and 59.9 parts of an emulsion dispersion of zinc stearate (b1) obtained in the same manner as in Example 1. Was charged into a mixing vessel, and stirred at 25 ° C. for 20 minutes with a paddle-type low-speed stirrer (peripheral speed: 100 m / min) to obtain an emulsified dispersion 6 of the present invention.
[0078]
<Example 7>
7.8 parts of an emulsified dispersion of maleic acid-modified polypropylene wax (a2) obtained as in Example 2 and 92.2 parts of an emulsified dispersion of magnesium palmitate (b3) obtained as in Example 3. Was charged into a mixing vessel and stirred at 25 ° C. for 20 minutes with a paddle-type low-speed stirrer (peripheral speed: 100 m / min) to obtain an emulsified dispersion 7 of the present invention.
[0079]
Example 8
2.7 parts of an emulsified dispersion of microcrystalline wax (a3) obtained as in Example 3 and 97.3 parts of an emulsified dispersion of zinc stearate (b1) obtained as in Example 1 were mixed. The emulsified dispersion 8 of the present invention was obtained by charging into a container and stirring at 25 ° C. for 20 minutes with a paddle-type low-speed stirrer (peripheral speed: 100 m / min).
[0080]
<Example 9>
A mixed container comprising 13.9 parts of an emulsified dispersion of microcrystalline wax (a3) obtained in the same manner as in Example 3 and 86.1 parts of an emulsified dispersion of calcium stearate (b2) obtained in the same manner as in Example 2. And the resulting mixture was stirred at 25 ° C. with a paddle-type low-speed stirrer (peripheral speed: 100 m / min) for 20 minutes to obtain an emulsified dispersion 9 of the present invention.
[0081]
With respect to the emulsified dispersions 1 to 9 of the present invention obtained in Examples 1 to 9, the water-insoluble wax (a) and the water-insoluble metal soap (b) used were mixed with the weight ratio of (a) and (b) (a / The results are shown in Table 1 together with the contents of b) and (a) and (b).
[Table 1]

[0082]
<Comparative Examples 1 to 6>
The emulsified dispersions of (a1), (a2) or (a3) and the emulsified dispersions of (b1), (b2) or (b3) were respectively referred to as emulsified dispersions 11 to 16 for comparison.
[0083]
For the emulsified dispersions 1 to 9 of the present invention (Examples 1 to 9) and the emulsified dispersions 1 to 6 for comparison (Comparative Examples 1 to 6), the volume average particle diameter, the substrate surface modifying ability (surface friction control) Performance and water resistance) were evaluated, and the results are shown in Table 2.
[0084]
<Comparative Examples 7 to 15>
As described in Table 2, the emulsified dispersions 1 to 6 for comparison were combined, and charged and mixed with the styrene-butadiene latex immediately before the evaluation of the substrate surface modifying ability, and then the substrate surface modifying ability was evaluated. The results are shown in Table 2.
[0085]
<Method of measuring volume average particle size>
Laser light diffraction scattering particle size distribution analyzer {trade name: MICROTRAC UPA, manufactured by Leads and Northerup), conditions (laser light wavelength: 780 nm, measurement temperature: 25 ° C., dispersion medium: water, measurement time 1 minute)} Was measured by
[0086]
<Surface friction adjusting ability>
A styrene-butadiene latex (trade name: JSR0696, manufactured by JSR) 200 g is weighed and placed in a 300 ml glass beaker (outer diameter 78 mm, height 103 mm), and a DC stirrer (coated with polyfluoroethylene resin, round and thin, outer diameter 8 mm, length) 10 g of the evaluation sample was added under stirring at a rotation speed of 300 rpm at a rotation speed of 25 mm, and the mixture was uniformly mixed by continuing stirring for 10 minutes. In Comparative Examples 7 to 15, 10 g of evaluation samples were uniformly mixed at the weight ratios shown in Table 2. That is, the first emulsified dispersion (upper row in Table 2) was charged with a DC stirrer under stirring at a rotation speed of 300 rpm, and stirred for 10 minutes. It was thrown in with a stirrer under stirring at a rotation speed of 300 rpm, and stirred for 10 minutes. This was coated on a high quality paper using a bar coater No. 8 and dried at 130 ° C. for 15 seconds and left for 24 hours to prepare a measurement sample. In addition, a measurement sample to which no evaluation sample was put was also prepared as a blank.
Subsequently, the coefficient of static friction of the surface of the measurement sample was measured using a surface measuring device (trade name: Tribogear type: 14DR, manufactured by Haydon) in an atmosphere at a temperature of 25 ° C. and a relative humidity of 60%. That is, the measurement sample was cut into two test pieces (test piece size: jig side: length 10 cm × width 3.5 cm, table side: length 24 cm × width 5 cm), and a 30 mm flat indenter was used as a measurement jig. With the coated surfaces of the test pieces facing each other and in contact with each other, a vertical load was 1 kg, and the sample was slid over a distance of 120 mm at a pulling speed of 200 mm / min to measure a static friction coefficient (μs).
[0087]
<Water resistance>
In a 300 ml glass beaker (outer diameter 78 mm, height 103 mm), weigh 200 g of styrene-butadiene latex (trade name: JSR0696, manufactured by JSR), adjust the temperature to 25 ° C., and add a DC stirrer (polyethylene fluoride). 30 g of an evaluation sample was introduced under agitation at a rotational speed of 300 rpm with a resin coating, a round thin shape, an outer diameter of 8 mm, and a length of 25 mm), and the mixture was uniformly mixed by continuing stirring for 10 minutes. In Comparative Examples 7 to 15, 30 g of evaluation samples were uniformly mixed at the weight ratios shown in Table 2. That is, the first emulsified dispersion (upper row in Table 2) was charged with a DC stirrer under stirring at a rotation speed of 300 rpm, and the mixture was stirred for 10 minutes. The mixture was charged with a stirrer under stirring at a rotation speed of 300 rpm, and stirred for 10 minutes. The obtained mixed solution was applied to a glass plate using a 3MIL (76.5 μm) film applicator in a clean bench, and dried at 25 ° C. for 24 hours to prepare a measurement sample. Further, as a blank, a measurement sample to which no evaluation sample was put was also adjusted. This measurement sample was immersed in deionized water at 25 ° C., and the time until the coating film of the measurement sample was whitened was measured.
[0088]
[Table 2]

[0089]
【The invention's effect】
The emulsified dispersion of the present invention exhibits extremely excellent substrate surface modifying ability (particularly, surface friction adjusting ability and water resistance) as compared with the conventional wax emulsified dispersion or fatty acid metal salt emulsified dispersion.

Claims (5)

A wax-metal soap composite emulsified dispersion comprising composite particles containing a poorly water-soluble wax (a) and a poorly water-soluble metal soap (b). The emulsified dispersion according to claim 1, wherein the weight ratio (a / b) of the hardly water-soluble wax (a) to the hardly water-soluble metal soap (b) is 0.04 to 4. The emulsified dispersion according to claim 1 or 2, wherein the composite particles have a volume average particle diameter of 0.01 to 60 µm. A method for producing a wax-metal soap composite emulsified dispersion containing composite particles composed of a poorly water-soluble wax (a) and a poorly water-soluble metal soap (b), wherein the emulsified dispersion (I) containing the particles composed of (a) And a water-based emulsified dispersion (II) containing particles of (b). The volume average particle diameter of the particles composed of the poorly water-soluble wax (a) is 0.01 to 20 μm, and the volume average particle diameter of the particles composed of the poorly water-soluble metal soap (b) is 0.01 to 20 μm. Production method.